Fabrication of metal-organic framework architectures with macroscopic size: A review

Metal-organic framework (MOFs) are potentially attractive porous materials for many industrial applications; however, they are not necessarily suitable for industrial scale implementations. MOFs are typically produced as polydisperse microcrystalline powders. Industrial applicability of MOF powders is limited by their mechanical, chemical and attrition resistance, mass transfer limitations, and/or poor handling properties. Formulating MOFs in macroscopic architectures is an essential step towards their successful implementations at industrial level. In this comprehensive Review, we extensively describe the most popular synthesis methods of macroscopic MOF architectures: mechanical densification, coordination replication, sol–gel approach, Pickering emulsion method, and 3D printing technology. The main objective of this Review is to systematize our knowledge about the synthesis methods of macroscopic MOF architectures. A thorough understanding of these synthesis techniques is expected to facilitate the preparation of innovative macroscopic MOF architectures. The excellent performance of macroscopic MOF architectures in comparison to polydisperse microcrystalline MOF powders is also revealed throughout the Review. Finally, we outline the advantages and drawbacks of each synthesis approach.